A tin-lead mixed perovskite liquid supply system and method of use thereof

Abstract

The tin-lead mixed perovskite liquid supply system and the use method thereof, which comprises a liquid preparation device, a storage device, a reduction device, a liquid supply device, a liquid supply device and a coating device, the storage device comprises a bubbling device and a metal mesh from bottom to top, the reduction device chamber is longitudinally provided with metal partition plates spaced apart from top to bottom, the liquid supply device comprises a first liquid supply device and a second liquid supply device, the second liquid supply device is a front end component of the liquid supply device, the left side of the liquid supply device is connected with the reduction device, and the right side of the liquid supply device is connected with the coating device. 4+ The method can maximize the Sn 2+ in the precursor liquid by prolonging the liquid supply path of the precursor liquid, so as to avoid the oxidation of Sn 2+ in the use process, effectively inhibit the oxidation of Sn 2+ in the perovskite precursor liquid supply process and the coating process, improve the stability of the tin-lead mixed perovskite precursor liquid and the crystallization stability in the coating process, and further improve the photoelectric conversion efficiency of the full calcium laminated perovskite battery.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of all-calcium tandem perovskite battery, and particularly relates to a tin-lead mixed perovskite liquid supply system and a use method thereof. BACKGROUND

[0002] With the rapid development of the photovoltaic industry, the industrialization efficiency of PERC cells has reached 23.5%, and is about to reach the efficiency limit of 24%. As a new darling of the photovoltaic industry, perovskite cells have undergone rapid development for 13 years, and the photoelectric conversion efficiency has increased from 3.8% to 25.7%, and the stability has also been greatly improved. The efficiency of perovskite / perovskite tandem cells (all-calcium tandem) is even higher than 28.0%, surpassing the record of 26.7% set by single-crystal silicon cells. Although small-area all-calcium tandem cells have achieved remarkable results, with the acceleration of the industrialization process of perovskite large-area, the stability defects of the perovskite cell preparation process limit its competition with traditional crystalline silicon cells in the photovoltaic power station field.

[0003] The all-calcium tandem perovskite cell is composed of a top cell and a bottom cell, and the top cell and the bottom cell absorb short-wave and long-wave light respectively. The top cell is prepared by tin-lead mixed narrow-bandgap perovskite material, and the bandgap is adjusted and optimized by adjusting the tin-lead ratio in the perovskite precursor solution. However, since the tin in the tin-lead mixed perovskite is +2 tin, it is easy to be oxidized to +4 valence in the air. In order to prevent Sn 2+ from being oxidized to Sn 4+ , the existing all-calcium tandem cell usually adds a reducing agent to the perovskite precursor solution to inhibit the oxidation of Sn 2+ , or deposits a barrier layer on the surface of the crystallized perovskite film to prevent the occurrence of oxidation reaction. However, the additive engineering and the barrier layer will inevitably cause the performance of the all-calcium tandem cell to decrease.

[0004] Therefore, how to avoid the oxidation of Sn 2+ to Sn 4+ in the precursor solution during the industrialization process has become the top priority of the all-calcium tandem cell. In addition to ensuring the stability of Sn 2+ in the precursor solution during storage, it is also particularly important to ensure the stability of the precursor solution during coating. The knife head of the traditional slot coating device is made of stainless steel. Once the precursor solution enters the slot coating device, it will start to oxidize, which will cause the morphology of the perovskite to change during crystallization.

[0005] The existing perovskite precursor solution supply system directly uses a liquid supply pump to quantitatively input the precursor solution into the coating device to realize film plating. For the tin-lead mixed perovskite system, due to the residual oxygen in the pipeline and the exposure of the coating device to the air, it is inevitable that Sn 2+oxidation, therefore the present application provides a tin-lead mixed perovskite liquid supply device to improve the prior art full calcium laminated battery manufacturing process Sn 2+ oxidation to Sn 4+ problems, improve the stability of tin-lead mixed perovskite precursor liquid and the crystallization stability during the coating process. SUMMARY

[0006] The purpose of the present application is to provide a tin-lead mixed perovskite liquid supply system to solve the problems of Sn 2+ oxidation and stability during the coating process.

[0007] Another purpose of the present application is to provide a method for using a tin-lead mixed perovskite liquid supply system.

[0008] The tin-lead mixed perovskite liquid supply system and its use method proposed by the present application, comprising: a liquid preparation device, a storage device, a reduction device, a liquid supply device, a liquid supply device and a coating device, the storage device comprises a bubbling device from bottom to top and a metal mesh, the reduction device chamber is longitudinally provided with upper and lower spaced metal partitions, the liquid supply device comprises a first liquid supply device and a second liquid supply device, the first liquid supply device is connected to the storage device on the left side and the reduction device on the right side, the second liquid supply device is located at the front end of the liquid supply device as a component of the liquid supply device, the end of the liquid supply device is provided with a concentration detection device and a filter device, and the left side of the liquid supply device is connected to the reduction device and the right side is connected to the coating device, the coating device is composed of a coating equipment and a substrate, the coating equipment mainly comprises a tool bit, the bubbling device is connected to the liquid preparation device, and the bubbling device is located at the bottom of the storage device, the prepared precursor liquid is transferred from the liquid preparation device to the storage device through the bubbling device by a liquid supply pump, the filter device is located at the rightmost side of the liquid supply device and plays a filtering role to prevent residues and incompletely dissolved precursors in the precursor liquid from entering the coating device and damaging the tool bit, the filter device has a pore size of 0.25-1um, the metal mesh is arranged above the bubbling device and is distributed in parallel at different positions of the storage device, and the metal mesh is made of one or more of potassium, calcium, barium, sodium, magnesium, aluminum, manganese, zinc, chromium, iron, cobalt, nickel and tin.

[0009] The liquid outlet hole of the bubbling device is one or a mixture of several of circular, rhombic, elliptical, triangular, trapezoidal and rectangular.

[0010] The right side of the storage device is the reduction device, the upper and lower spaced metal partitions longitudinally arranged in the chamber of the reduction device are parallel and spaced, and the number of partitions is any value between 1 and n.

[0011] The right side of the reduction device is the liquid supply device, the liquid supply device further comprises a catheter, and the right side of the catheter is provided with a concentration detection device. The concentration detection device can detect Sn2+ Sn 4+ ion concentration.

[0012] The inner coating of the conduit is an alloy of one or more of potassium, calcium, barium, sodium, magnesium, aluminum, manganese, zinc, chromium, iron, cobalt, nickel, tin, and can also be a metal conduit of the above-mentioned metal materials.

[0013] The coating device is provided on the right side of the liquid supply device, and a manifold is further provided in the inner part of the coating device cutter head. The inner part of the coating device cutter head and the manifold are plated with a metal coating, which is an alloy of one or more of potassium, calcium, barium, sodium, magnesium, aluminum, manganese, zinc, chromium, iron, cobalt, nickel, and tin.

[0014] A method for using a tin-lead mixed perovskite liquid supply device, comprising the following steps:

[0015] S1. The liquid supply system comprises a liquid preparation device, a storage device, a reduction device, a liquid delivery device, a liquid supply device, and a coating device. The storage device comprises a bubble device and a metal mesh from bottom to top. The precursor liquid prepared in the liquid preparation device is introduced into the storage device through the bubble device. The gas outlet of the bubble device is circular, and the diameter of the bubble opening is 1 / 10 of the width of the storage device, and the bubble openings are uniformly distributed. The metal mesh is a tin mesh. At this time, if Sn 4+ exists in the precursor liquid, the reaction Sn 4+ + Sn = 2Sn 2+ will occur, and Sn 4+ will be reduced to Sn 2+ ;

[0016] S2. The precursor liquid in the storage device is introduced into the reduction device through the liquid delivery device. Tin plates are vertically arranged in the chamber of the reduction device with an upper and lower interval. The interval width of the tin plates is 1 / 10 of the width of the reduction device, and the partitions are uniformly distributed. At this time, if Sn 4+ exists in the precursor liquid, the reaction Sn 4+ + Sn = 2Sn 2+ will occur, and Sn 4+ will be reduced to Sn 2+ ;

[0017] S3. The precursor liquid in the reduction device is introduced into the coating system through the tinned conduit by the liquid supply device. The concentration detection device is used to detect Sn 4+ in the precursor liquid. The pore size of the filter device is 0.25um. At this time, if Sn 4 + exists in the precursor liquid, the reaction Sn 4+ + Sn = 2Sn 2+ will occur, and Sn 4+ will be reduced to Sn 2+ ;

[0018] S4. The precursor liquid is introduced into the coating device by the liquid supply system, the inside of the cutter head of the coating device is provided with a tin plating protective layer, including the inside of the manifold is provided with a tin plating protective layer, at the same time, if Sn 4+ exists in the precursor liquid, the reaction of Sn 4+ + Sn = 2 Sn 2+ will occur, Sn 4+ is reduced to Sn 2+ .

[0019] The tin-lead mixed perovskite liquid supply system and the use method thereof provided by the application change the existing equipment, add a storage device, a reduction device, a liquid supply device and a coating device, the method prolongs the precursor liquid delivery path, and Sn 4+ in the precursor liquid is maximally reduced to Sn 2+ , so as to avoid the oxidation of Sn 2+ during use, can inhibit the oxidation of Sn 2+ in the perovskite precursor liquid supply process and the coating process, improve the stability of the tin-lead mixed perovskite precursor liquid and the crystallization stability in the coating process, and further improve the photoelectric conversion efficiency of the full calcium stacked perovskite battery. BRIEF DESCRIPTION OF DRAWINGS

[0020] The accompanying drawings are provided for the logic principle diagram of the tin-lead mixed perovskite liquid supply system and the use method thereof provided by the application. Figure 1 The accompanying drawings are provided for the logic principle diagram of the tin-lead mixed perovskite liquid supply system and the use method thereof provided by the application. DETAILED DESCRIPTION

[0021] Referring to Figure 1 , the figure shows the overall structure of the tin-lead mixed perovskite liquid supply system and the use method thereof provided by the application. The liquid supply system comprises a liquid preparation device 1, a storage device 2, a reduction device 3, a liquid delivery device 4, a liquid supply device 5 and a coating device 6, the storage device 2 comprises a bubbling device 21 and a metal mesh 22 from bottom to top, the reduction device 3 is longitudinally provided with metal partition plates 31 spaced apart from top to bottom in the chamber, the liquid delivery device 4 comprises a first liquid delivery device 41 and a second liquid delivery device 42, the left side of the first liquid delivery device 41 is connected with the storage device 2, the right side is connected with the reduction device 3, the second liquid delivery device 42 is located at the front end of the liquid supply device 5 as a component part of the liquid supply device 5, the end of the liquid supply device 5 is provided with a concentration detection device 53 and a filtering device 54, the left side of the liquid supply device 5 is connected with the reduction device 3, and the right side is connected with the coating device 6, the coating device 6 mainly comprises a coating cutter head 61 and a substrate 62 provided on the coating equipment.

[0022] As Figure 1As shown, preferably, the leftmost side of the liquid supply system is the storage device 2; the bubbling device 21 is connected to the liquid preparation device 1 below the storage device, the bubbling device 21 is located at the bottom of the storage device 2, and the liquid preparation device 1 transfers the prepared precursor liquid 11 to the storage device 2 through the bubbling device 21 by the liquid supply pump. The storage device 2 is composed of the bubbling device 21, the metal mesh 22 and the precursor liquid 11, and the outlet of the bubbling device 21 is preferably circular, the outlets are uniformly distributed, and the diameter of the outlets is 1 / 10 of the width of the storage tube body;

[0023] The metal mesh 22 is arranged above the bubbling device 21 and is sequentially and parallelly distributed at different positions of the storage device 2, wherein the material of the metal mesh 22 is preferably tin mesh.

[0024] The right side of the storage device 2 is the reduction device 3, and the chamber of the reduction device 3 is longitudinally provided with upper and lower spaced metal partitions 31, the metal partitions 31 are parallelly and spaced, the number of the metal partitions 31 is 9, and further, the material of the metal partitions 31 is tin plate.

[0025] Preferably, the right side of the reduction device 3 is the liquid supply device 5, and further, the liquid supply device 5 is composed of a second liquid supply device 42, a catheter 52, a concentration detection device 53 and a filtering device 54; further, the inner coating of the catheter 52 is tin;

[0026] The second liquid supply device 42 is located at the front end of the liquid supply device 5 and supplies liquid to the coating device 6;

[0027] Further, the concentration detection device 53 is located at the right side of the catheter 52 and is used to detect the ion concentration of Sn 4+ ;

[0028] Further, the filtering device 54 is located at the rightmost side of the liquid supply device 4 and plays a filtering role to prevent residues and incompletely dissolved precursors in the precursor liquid 11 from entering the coating device 6 and damaging the tool bit 61, and the pore size of the filtering device is 0.25um.

[0029] Preferably, the right side of the liquid supply device 5 is the coating device 6, and further, the tool bit 61 of the coating device 6 is plated with a metal coating 63, and further, the metal coating 63 is uniformly tin, and the tool bit 61 further includes a manifold 64, and the inner part of the manifold 64 is also entirely plated with a tin protective layer.

[0030] In use, step S1, the prepared precursor liquid is introduced into the storage device through the bubbling device in the liquid preparation device, preferably, the gas outlet of the bubbling device is circular, the diameter of the bubbling port is 1 / 10 of the width of the storage device, and the bubbling ports are uniformly distributed, and the metal mesh 22 is a tin mesh, at this time, if Sn 4+ exists in the precursor liquid, Sn 4++ Sn = 2 Sn 2+ reaction, Sn 4+ is reduced to Sn 2+ ;

[0031] S2. The precursor liquid in the storage device is introduced into the reduction device through the infusion device, preferably, tin plates are arranged in the reduction device, the interval width is 1 / 10 of the width of the reduction device, and the partitions are uniformly distributed. At this time, if Sn 4+ exists in the precursor liquid, Sn 4+ + Sn = 2 Sn 2+ reaction, Sn 4+ is reduced to Sn 2+ ;

[0032] S3. The precursor liquid in the reduction device is introduced into the coating system through the tinning conduit through the liquid supply device, preferably, the concentration detection device is used to detect Sn 4+ in the precursor liquid, the pore size of the filter device is 0.25 um, and at this time, if Sn 4+ exists in the precursor liquid, Sn 4+ + Sn = 2 Sn 2+ reaction, Sn 4+ is reduced to Sn 2+ ;

[0033] S4. The precursor liquid is introduced into the coating device through the liquid supply system, the inside of the tool bit of the coating device adopts a tinned protective layer, the inside of the manifold adopts a tinned protective layer, and at this time, if Sn 4+ exists in the precursor liquid, Sn 4+ + Sn = 2 Sn 2+ reaction, Sn 4+ is reduced to Sn 2+ .

[0034] The application increases the storage device 2, the reduction device 3, the infusion device 4, the liquid supply device 5 and the coating device 6 on the basis of the original equipment, all the parts in the liquid supply device 5 which contact the precursor liquid 11 adopt a more active metal or a plated layer of the metal, which plays a role in inhibiting Sn 2+ oxidation, the storage device 2 adopts a bubbling device 21 matched with a metal mesh 22, which can effectively increase the reaction degree of Sn 4+ in the precursor liquid 11 with the metal mesh 22, and promote the reduction of Sn 4+ ; the multiple metal partitions 31 arranged in the reduction device 3 can also reduce the residual Sn 4+ in the precursor liquid 11, and minimize the concentration of Sn 4+ ; a metal protective layer is prepared in the inside of the coating tool bit 61 in the coating device 6, which can inhibit Sn 2+oxidized to Sn 4+， The above reduction reaction equation is: Sn 4+ + Sn = 2 Sn 2+ The method maximizes the Sn 4+ reduction to Sn 2+ to avoid the oxidation of Sn 2+ during use, effectively inhibiting the oxidation of Sn 2+ during the supply of perovskite precursor solution and the coating process, improving the stability of the tin-lead mixed perovskite precursor solution and the crystallization stability during the coating process, and further improving the photoelectric conversion efficiency of the full perovskite stacked perovskite battery.

[0035] The above-described embodiments are merely preferred embodiments of the present application and are not intended to limit the scope of the present application. Various modifications and improvements to the technical solutions of the present application made by those of ordinary skill in the art without departing from the design spirit of the present application shall fall within the scope of protection of the present application as defined by the claims.

Claims

1. A tin-lead mixed perovskite liquid supply system characterized by: The liquid supply system comprises a liquid preparation device, a storage device, a reduction device, a liquid delivery device, a liquid supply device and a coating device. The storage device comprises a bubble device and a metal mesh arranged from bottom to top. The reduction device is longitudinally provided with metal partitions spaced vertically in the chamber. The liquid delivery device comprises a first liquid delivery device and a second liquid delivery device. The first liquid delivery device is connected to the storage device on the left side and connected to the reduction device on the right side. The second liquid delivery device is located at the front end of the liquid supply device as a component of the liquid supply device. The liquid supply device is provided with a concentration detection device and a filter device at the end. The liquid supply device is connected to the reduction device on the left side and connected to the coating device on the right side. The coating device is composed of a coating device and a substrate. The coating device mainly comprises a tool bit. The bubble device is connected to the liquid preparation device and located at the bottom of the storage device. The liquid preparation device transfers the prepared precursor liquid to the storage device through the bubble device by a liquid supply pump. The filter device is located at the rightmost side of the liquid supply device and plays a filtering role to prevent residues and incompletely dissolved precursors in the precursor liquid from entering the coating device to damage the tool bit. The filter device has a pore size of 0.25-1um. The metal mesh is arranged above the bubble device and is distributed in parallel at different positions of the storage device. The metal mesh is made of one or more of potassium, calcium, barium, sodium, magnesium, aluminum, manganese, zinc, chromium, iron, cobalt, nickel and tin. The coating device is located on the right side of the liquid supply device. The coating device is provided with a manifold inside the tool bit. The tool bit and the manifold are both plated with a metal coating. The metal coating is an alloy of one or more of potassium, calcium, barium, sodium, magnesium, aluminum, manganese, zinc, chromium, iron, cobalt, nickel and tin.

2. The tin-lead mixed perovskite liquid supply system according to claim 1, characterized in that: The bubble device outlet hole is one or a mixture of several of circular, rhombic, oval, triangular, trapezoidal and rectangular.

3. The tin-lead mixed perovskite liquid supply system according to claim 1, characterized in that: The storage device is provided with the reduction device on the right side. The vertically spaced metal partitions longitudinally arranged in the chamber of the reduction device are parallel and spaced. The number of metal partitions is an arbitrary value between 1 and n.

4. The tin-lead mixed perovskite liquid supply system according to claim 1, characterized in that: The reducing device right side is for liquid device, the liquid device also includes catheter, catheter right side is concentration detection setting, the concentration detection device can single or simultaneously detect Sn 2+ , Sn 4+ Ion concentration.

5. The tin-lead mixed perovskite liquid supply system according to claim 4, characterized in that: The inner coating of the catheter is an alloy of one or more of potassium, calcium, barium, sodium, magnesium, aluminum, manganese, zinc, chromium, iron, cobalt, nickel and tin. It can also be a metal catheter made of the above metal materials.

6. A method of using a tin-lead mixed perovskite liquid supply system according to any one of claims 1-5, characterized in that The method comprises the following steps: S1. The precursor solution prepared in the liquid preparation device is introduced into the storage device through the bubbling device. The gas outlet of the bubbling device is circular, the diameter of the bubbling port is 1 / 10 of the width of the storage device, and the bubbling ports are uniformly distributed. The metal mesh is a tin mesh. At this time, if Sn 4+ exists in the precursor solution, Sn 4+ + Sn = 2 Sn 2+ will react, and Sn 4+ will be reduced to Sn 2+ . S2. The precursor liquid in the storage device is introduced into the reduction device through the first infusion device. The tin plates are longitudinally arranged and spaced vertically in the chamber of the reduction device. The spacing width of the tin plates is 1 / 10 of the width of the reduction device. The tin plates are uniformly distributed. At the same time, if Sn 4+ exists in the precursor liquid, the following reaction will occur: 4+ Sn + Sn = 2Sn 2+ , and Sn 4+ is reduced to Sn 2+ ; S3. The precursor solution in the reducing device is introduced into the coating device through the tinning conduit by the liquid supply device, and the concentration detection device is used to detect Sn in the precursor solution 4+ , the filter device has a pore size of 0.25 um, and at this time, if Sn exists in the precursor solution 4+ , the reaction of Sn 4+ + Sn = 2 Sn will occur, and Sn 2+ will be reduced to Sn 4+ ; and 2+ ​ S4. The precursor liquid is introduced into the coating device by the liquid supply device, and a tin plating protective layer is used inside the cutter head of the coating device, including the entire manifold inside. At this time, if Sn 4+ exists in the precursor liquid, the following reaction will occur: 4+ Sn+Sn=2Sn 2+ , and Sn 4+ will be reduced to Sn 2+ .

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